Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials, Friedrich-Alexander-University Erlangen-Nuremberg, Erlangen 91058, Germany.
Nanoscale. 2016 Jul 21;8(27):13257-62. doi: 10.1039/c6nr03324e. Epub 2016 Jun 23.
A newly designed electron donor-acceptor conjugate, namely Ce2@Ih-C80-H2P consisting of an endohedral dimetallofullerene Ce2@Ih-C80 and a free-base prophyrin (H2P), has been synthesized and systematically investigated. Basic characterization by means of NMR spectroscopy, steady-state absorption spectroscopy, and electrochemistry points to a folded configuration with sizeable interactions between Ce2@Ih-C80 and H2P. Complementary DFT optimization also results in the same conclusions. Time-resolved absorption spectroscopic investigations corroborate the formation of the (Ce2)˙(-)@Ih-C80-(H2P)˙(+) radical ion pair state in non-polar as well as polar media. Overall, the modus operandi is an ultrafast through-space electron transfer enabled by the folded configuration in the ground and excited state.
一种新设计的电子给体-受体共轭物，即 Ce2@Ih-C80-H2P，由内包二金属富勒烯 Ce2@Ih-C80 和自由碱基卟啉（H2P）组成，已被合成并进行了系统研究。通过 NMR 光谱、稳态吸收光谱和电化学手段进行的基本表征表明，Ce2@Ih-C80 和 H2P 之间存在折叠构象和相当大的相互作用。互补的 DFT 优化也得出了相同的结论。时间分辨吸收光谱研究证实了（Ce2）˙(-)@Ih-C80-(H2P)˙(+)自由基离子对态在非极性和极性介质中的形成。总的来说，这种操作模式是通过在基态和激发态下的折叠构象实现的超快通过空间电子转移。
